Hair spray compositions

ABSTRACT

Hair spray compositions containing a carboxylated polyurethane resin, and having a low volatile organic content, are disclosed. The compositions have a low viscosity, and can be applied as a pump spray or as an aerosol, to hold the hair and impart excellent hair set retention properties. The hair spray compositions can be used with a curling iron or a blow dryer to style the hair.

FIELD OF INVENTION

[0001] The present invention is directed to hair spray compositions thatare applied to the hair to maintain the hair in a predetermined shape orconfiguration. The compositions impart excellent hair set retention,fell, and washability to sprayed hair. In particular, the presentinvention relates to aerosol and nonaerosol hair spray compositionscomprising a carboxylated polyurethane resin, an organic solvent, andwater, wherein the composition preferably is free of a neutralizingagent for the polyurethane resin.

BACKGROUND OF THE INVENTION

[0002] Normal hair can be so fine, limp, and lacking in body that thehair does not hold a hair set well. Furthermore, hair can lose body andbe weakened as a result of being subjected to chemically active hairtreatments, such as permanent waves and tints. Additionally, hair can beweakened even further by other contributing factors, such as bleachingby the sun or chlorinated swimming pool water.

[0003] Hair setting is basically the process of shaping wet hair by thesteps of stretching the hair by curling the hair, fixing the hair inplace by drying, then combing to give the finishing touches to providethe desired hairstyle. In particular, the setting of wet hair can beaccomplished by making flat curls from strands of hair and fixing thecurls with hairpins to product “pin curls.” Similarly, the wet hair canbe set by using any of a variety of rollers or curlers to mechanicallyfix the hair. In either case, winding of the wet hair is followed bydrying, either ambient air drying, electric drying, or hot air, i.e.,blow, drying.

[0004] The inherent problem encountered in hair setting is the naturaltendency of hair to return to its natural shape. For example, set hairreturns to its natural shape almost immediately if moistened. Likewise,high humidity conditions accelerate the tendency of hair to return toits natural shape. Therefore, intensive efforts have been directedtoward providing a hair set with sufficient holding power to maintain adesired hairstyle until at least the next shampoo, and, therefore,giving the hair set a degree of permanency.

[0005] As indicated by the natural tendency of hair to return to itsnatural shape, hair is an elastic structure. As a result, slightdeformations in hair structure resulting from setting the hair arecompletely reversible. However, the rate of return of hair to itsnatural shape as dependent upon the method used to deform, or set, thehair. Hair sets performed on wet strands of hair being rolled tightly,either in curls around the finger or on curlers, followed by drying thehair and unrolling the curlers after drying, corresponds to the releaseof the hair from a deformation-causing load. The deformation, or set,obtained can last for several days, but the set will not be retained ifthe hair is wetted.

[0006] Investigators have sought to delay the combined action of naturalforces and moisture that cause hair to return to its original state byapplying solutions containing naturally occurring or synthetic polymersafter the hair is shaped into a desired configuration. When applied toshaped hair from aqueous or aqueous/alcoholic solutions, the polymersform a film on the hair, after drying, to help maintain the hair in thepreviously shaped configuration. The polymeric film promotes cohesionand gives stability to the hair set to maintain hold of the set. Theprincipal objective of a setting lotion is to cover the previouslystyled hair with an invisible polymeric film that gives styled hair adegree of rigidity and protects the hairstyle against wind and humidity.

[0007] Hair spray products act in a similar manner. Hair spray productsare applied to wet and/or dry hair and contain a polymer, or polymermixture, that remains fixed on the previously styled hair and effectsthe hair in various ways. For example, a “mechanical” effect is exertedon each individual hair. The film-forming polymers are used to provide aflexible sheath of polymeric film on the shaped hair after drying, and,therefore, for mechanical reasons, retard the return of each individualhair to its natural shape. In addition, the polymeric film provides anoverall stiffening of the hair. The hair behaves as if the individualhair strands are welded together, and the final hairstyle has bettercohesion, therefore, resisting the natural forces that return the hairto its natural shape. Finally, the polymeric film protects the hair fromhumidity. The ability of the polymeric film to attract and absorb waterpreferably is minimal, such that the polymeric film retards moistureuptake by hair and retards the return of the hair to its natural state.

[0008] The general principles of hair setting are thoroughly discussedby C. Zviak, in The Science of Hair Care, Marcel Dekker, pp. 149-181(1986). Zviak reviews both the polymers used in hair setting productsand the formulation principles used to produce a hair set product thatprovides such beneficial hair set properties as improved hairstyle hold,easy application and combing, quick drying and nonstickiness, good hairbody and bounce, increased hair volume and gloss, and hydrophobicity. Itis evident that in the formulation of any end-use hairstyling product,some of these benefits must be sacrificed to some degree to achieve acompeting benefit. Therefore, the formulation of hair set products hasproved difficult.

[0009] As a result, to overcome some of the inherent disadvantages ofthe polymers utilized to set the hair, hair set products are madeavailable in diversified forms in an attempt to minimize the drawbacksof the particular polymer used in the formulation. For example, hair setproducts are available as plasticizing lotions, plasticizing gels,aerosol foams, all-purpose lotions, hair sprays, holding lotions,conditioners, and shampoos.

[0010] Nonionic, cationic, and anionic polymers have been used in hairset products, with the anionic polymers providing the best hair setresults. However, anionic polymers also have disadvantages, such as highwater solubility, and, therefore, low hydrophobicity, and lowsubstantivity on hair fibers, and, therefore, causing a crust andflaking due to easy elimination from the hair by combing and brushing.As a result, investigators have continued to search for compounds andcompositions that provide the primary benefit of improved durability ofthe hair set.

[0011] Therefore, the use of resins, or polymers, in hair sprays is wellknown, as summarized in Grollier et al. U.S. Pat. No. 4,445,521. Theresins typically used in hair sprays are linear vinyl (e.g., an alkylvinyl ether) or acrylic (e.g., an alkyl acrylate) polymers prepared bycopolymerizing two or more monomers in a free radical polymerizationreaction. The vinyl and acrylic-based resins are used in relatively highconcentrations in a hair spray composition to fix the hair in aparticular configuration and to provide good hair set retention.However, at high concentrations, the vinyl and acrylic-based resinsexhibit disadvantages that adversely affect the hair, such as poorcombing and feel, and excessive stiffness, crust, and flaking.

[0012] The vinyl and acrylic-based hair fixative resins typically usedin hair sprays were designed for use in anhydrous alcoholic hair spraycompositions. The resins, therefore, have excellent compatibility with,and solubility in, alcohols (e.g., ethanol) used in pump spraycompositions and hydrocarbons used as propellants in aerosolcompositions. However, due to environmental and toxicological concerns,government regulations require a decrease in the amount of organicsolvents used in hair spray and related compositions. Therefore, thealcohols and the hydrocarbon gases traditionally present in hair spraycompositions are being replaced by water and water-soluble solvents,like dimethyl ether, that pose less harm to the environment.

[0013] The solvent changes required by government regulation made thetraditional vinyl and acrylic-based resins unsuitable in hair spraycompositions.

[0014] For example, the presence of water in a hair spray compositionincreases the viscosity of the composition, thereby making sprayingdifficult to impossible when traditional resins are used. The relativelyhigh viscosity of the compositions, therefore, requires a reduction inthe resin concentration of the composition, which, in turn, results ininsufficient hair set retention. The presence of water also increasesthe tackiness of the resin on the hair, thereby prolonging the dryingtime of the hair spray on the hair. Water also reduces the hair-wettingability of the compositions, resulting in beading and flaking of theresin from the hair. In the case of aerosol products, the combination ofwater, resin, and propellant gas results in poor delivery and foaming ofthe composition, large aerosol particle size, and beading of the resin.

[0015] The need to change solvent systems for hair sprays again ledinvestigators to search for new hair setting resins that overcome thedisadvantages associated with the vinyl and acrylic resins. As set forthin European Patent Application 0 619 111, one class of resins is thepolyurethanes. However, the hair fixative compositions disclosed in EP 0619 111 require a base to neutralize, and solubilize, the polyurethaneresin. It would be desirable to provide an aqueous hair spraycomposition containing a low amount of volatile organic compounds (VOC),that is free of a base, and that overcomes that disadvantages associatedwith traditional vinyl and acrylic resins.

SUMMARY OF THE INVENTION

[0016] The present invention is directed to aerosol and nonaerosol(i.e., pumpable) hair spray compositions containing hydrophilic,carboxylated polyurethane resins. The hair spray compositions impartgood hair set retention and natural feel to sprayed hair, and providesuperior retention of the hairstyle at high relative humidity. Suchresults are unexpected because traditional hair fixative resins arehydrophobic. In contrast, the carboxylated polyurethane resins arehydrophilic, yet provide a soft, natural feel to the hair, and the hairis not tacky.

[0017] The carboxylated polyurethane resins are soluble in a wide rangeof water-to-alcohol ratios, without the need to neutralize the resinwith a base. Therefore, the hair spray compositions contain a low amountof VOC and are safe to the environment.

[0018] In particular, the present invention is directed to hair spraycompositions comprising: (a) about 0.25% to about 6%, by total weight ofthe composition, of a carboxylated polyurethane resin, (b) 0% to about80%, by total weight of the composition, of an alcohol, like ethanol,and (c) about 15% to about 80%, by total weight of the composition, ofwater. The hair spray compositions have a pH of about 6 to about 10.

[0019] The composition can be applied to the hair as a pump spray.Alternatively, If an aerosol composition is desired, the composition canfurther comprise about 5% to about 30%, by total weight of thecomposition, of a propellant. Optional ingredients also can beincorporated into the hair spray composition.

[0020] The polyurethane resins, also termed polycarbamyl polyglycols,have pendant carboxyl groups and are hydrophilic. The polyurethaneresins have improved tear strength, excellent washability, goodadhesion, and are soluble in water and polar solvents, thereby makingthem useful in hair spray compositions. In addition, the polyurethaneresins form clear, low viscosity, solutions in neutral to slightly basicaqueous solvents. Solutions of the hydrophilic polyurethane resins,therefore, are sprayable.

[0021] In accordance with an important aspect of the present invention,hair spray compositions exhibit excellent sprayability when theviscosity of a 55% by weight VOC composition is about 1 to about 10 cpsor about 1 to about 25 cps for an 80% by weight VOC composition.Compositions having such a viscosity provide a spray particle size ofabout 20 to about 150 microns.

[0022] In accordance with another important aspect of the presentinvention, the hair spray compositions exhibit improved washability fromthe hair when the carboxylated polyurethane resin has an acid value ofat least 7 mg KOH/g (milligram potassium hydroxide per gram of resin),and preferably about 7 to about 50 mg KOH/g of resin. The polyurethaneresins do not require neutralization with a base to provide a usefulhair spray composition.

[0023] In accordance with one embodiment of the present invention, thecarboxylated polyurethane resin used in the hair spray composition isproduced by reacting: (a) a diol component comprising a polyoxyalkylenediol; (b) an alkylene glycol; (c) a diisocyanate; (d) water in an amountof about 0.001% to about 0.95% of the combined weight of the reactants;and (e) a 2,2-di(hydroxymethyl)alkanoic acid, preferably2,2-di(hydroxymethyl)propionic acid, wherein the ratio of NCO(isocyanate) groups to OH (hydroxyl) groups in the water, diol, andglycol mixture, i.e., the R-value, is about 0.4 to about 1.1.

[0024] The hydrophilic carboxylated polyurethane resin containspolyoxyalkylene units, i.e., soft segments, and alkylene units, i.e.,hard segments, connected through urethane linkages. Also incorporatedinto the polymer chain is a small amount of diol having a pendantcarboxyl group. The polymer chain also contains urea linkages resultingfrom a reaction between the water and isocyanate groups, which modifythe hair styling properties of the polyurethane.

[0025] The polyoxyethylene soft segments of the polyurethane resinimpart hydrophilicity to the polyurethane. Soft segments derived frompolyoxypropylene and polyoxytetramethylene diols provide a softer, butless hydrophilic, polyurethane. Hydrophilic polyurethane resins havingimproved strength and superior adhesive properties can be formed byusing mixtures of polyoxyalkylene diols.

[0026] In another embodiment of the present invention, the carboxylatedpolyurethane resins used in the hair spray composition are produced from(a) a major portion of polyoxyethylene diol having a number molecularweight (M_(n)) of 6000 to 10,000;, (b) an alkylene glycol, preferablydiethylene glycol, cyclohexanedimethanol, or dipropylene glycol; (c) adiisocyanate; (d) water in the amount of about 0.01% to about 0.8% byweight; and (e) a 2,2-di-(hydroxymethyl) alkanoic acid, wherein theratio of NCO to OH in the water, diol, and glycol mixture (i.e., theR-value) is about 0.4 to about 0.98. These polyurethane resins aresoluble in dilute (neutral to basic) aqueous solutions, and exhibit goodspray-ability, superior feel, low flaking, desirable crust, and good setretention when applied to hair. The polyurethane resins are hydrophilic,and provide a soft feel in a hydrated state. In a particular embodimentof a polyurethane resin produced with a major portion of polyoxyethylenediol, water is added in the amount of about 0.04% to about 0.25% byweight, and the ratio of NCO to OH of the water, diol and glycol mixture(i.e., the R-value) is about 0.55 to about 0.98 to provide acarboxylated polyurethane resin having improved adhesiveness to the hairand improved slip on the hair, i.e., good combing properties.

[0027] Another aspect of the present invention is to provide a hairspray composition that provides good hair set retention at high relativehumidity and that imparts a natural feel to the hair. Accordingly, ahydrophilic polyurethane resin incorporated into a present hair spraycomposition has a weight average molecular weight (M_(w)) of about15,000 to about 150,000, and preferably about 15,000 to about 100,000.The polyurethane resins also have a polydispersibility index (PDI) ofabout 1 to about 4, and preferably about 1 to about 3. Preferredpolyurethane resins have an R-value of about 0.5 to about 1.

[0028] In accordance with another important aspect of the presentinvention, hair spray compositions of the present inventionincorporating a carboxylated polyurethane resin having an M_(w) greaterthan 30,000 impart a set retention of 62% or higher at 70% and 85%relative humidity. Hair spray compositions incorporating a polyurethaneresin having an M_(w) below 64,000 provide a hair curl compression inthe range between 133 to 296 gram force. In addition, hair spraycompositions incorporating a carboxylated polyurethane resin having anM_(w) below 64,000 further improves hair hand feel. A polyurethane resinhaving an M_(w) less than 40,000 and R-value less than 0.75 providessprayed hair having the best feel and the least amount of flaking.

DETAILED DESCRIPTION OF THE INVENTION

[0029] The present hair spray compositions are sprayable hair stylingaids containing a carboxylated polyurethane resin. The polyurethaneresins are soluble in water and in a broad range of water/alcoholmixtures, thereby permitting the preparation of aerosol and nonaerosol,i.e., pump spray, compositions containing a reduced amount of volatileorganic compounds (VOC). The hair spray compositions also can containpropellant gases, and can be applied as an aerosol spray. Thecarboxylated polyurethane resins possess thermal properties that allowstyling of the hair with curling irons or a blow dryer. The polyurethaneresin-based hairstyle compositions, therefore, overcome problems anddisadvantages associated with prior acrylic and vinyl-based hairfixative resins, and provide improved styling, hair set retention, hairfeel, washability, and spray properties.

[0030] In particular, the present hair spray compositions comprise about0.25% to abound 6%, and preferably about 0.5% to about 6%, by totalweight, so a carboxylated polyurethane resin. To achieve the fulladvantage of the present invention, the composition comprises about 1%to about 5%, by weight of the composition, of a carboxylatedpolyurethane resin.

[0031] The polyurethane resins are linear, hydroxyl-terminatedcopolymers having pendant carboxylic acid groups. In accordance with animportant feature of the present invention, the polyurethane resins canbe solubilized in water, or in a hydroalcoholic solution, in the absenceof a base.

[0032] The carboxylated polyurethane resins are soft and flexible, andhave a melting point of about 40° C. to about 120° C., and preferablyabout 60° C. to about 100° C. To achieve the full advantage of thepresent invention, the polyurethane resins have a melting point of about70° C. to about 90° C.

[0033] The carboxylated polyurethane resins also are (a) sprayable, (b)soluble in hydroalcoholic solutions, (c) propellant tolerant, and (d)fast drying. The polyurethane resins also exhibit good wet combingproperties, and are washable from the hair.

[0034] A polyurethane resin incorporated into a present hair spraycomposition comprises a reaction product of a diol component, analkylene glycol, an aliphatic diisocyanate, water, and a2,2-di-(hydroxymethyl) alkanoic acid. An amine, such as diglycolamine,can be substituted for at least a portion of the water in the reactionmixture. Aqueous solutions of the hydrophilic carboxylated polyurethaneresins have low viscosities, and impart a soft feel, good set retention,reduced flaking and crust, and improved hair conditioning properties tosprayed hair.

[0035] In one embodiment, the polyurethane resin comprises the reactionproduct of: a diol component comprising a polyoxyalkylene diol,preferably a polyoxyethylene diol having an M_(n) of about 400 to about20,000, a polyoxypropylene diol having an M_(n) of about 200 to about2500, a block copolymer of ethylene oxide and propylene oxide having anM_(n) of about 1,000 to about 9,000, or a polyoxytetramethylene diolhaving an M_(n) of about 200 to about 4,000; about 0.01% to about 10% byweight of a low molecular weight alkylene glycol selected from the groupconsisting of ethylene glycol, propylene glycol, 2-ethyl-1,3-hexanediol,tripropylene glycol, triethylene glycol, 2,4-pentanediol, 2-methyl-1,3-propanediol, 2-methyl-1, 3-pentanediol, cyclohexanediol,cyclohexanedimethanol, dipropylene glycol, diethylene glycol, andmixtures thereof; an organic diisocyanate; a 2,2-di-(hydroxymethyl)alkanoic acid; and water in an amount of about 0.001% to about 0.95% byweight of the reaction mixture, wherein the NCO/OH ratio (i.e., theR-value) is about 0.4 to about 1, and preferably about 0.4 to about 1.To achieve the full advantage of the present invention, the R-value isabout 0.5 to about 0.98.

[0036] An amine can be used in the reaction mixture for at least aportion of the water. The amine can be added to the reaction mixture inan amount of about 0.01% to about 0.8 by weight amine, preferably about0.02% to about 0.5% amine to about 0.01% to about 0.2% water in thereaction mixture. Amines that can be used in the reaction mixture areethylenediamine, propylenediamine, monoethanolamine, diglycolamine, andJEBFFAMINE D1-230, D-400, D-2000, D-4000, ED-0600,

[0037] ED-900, or ED-2001. The hydroxylamines and the JEFFAMMINEproducts are manufactured by Texaco Chemical Company. Preferably, theamine is a hydroxylamine, and most preferably the amine ismonoethanolamine and/or diglycolamine.

[0038] The polyoxyethylene diols are available from Union CarbideCorporation under the trademark CARBOWAX, such as CARBOWAX® 8000 andCARBOWAX® 1450 wherein the number represents number average molecularweight. The polyoxypropylene diols (PPG) are available from varioussources, such as the PPG series of ARCO NIAX® PPG 1025, PPG 425, PPG725, PPG 1225 and PPG 2025 and as R2134 (2200) and R2135 (4400), whereinthe number represents number average molecular weight. Triols are alsoavailable from ARCO as NIAX® Polyols 11-34, LG-650, LG-56, LG-168,LHT-28, LHT-240. The polyoxytetramethylene diols are available from E.I. DuPont de Nemours as TERATHANE 600, 1000, 1400, 2000, and 2900.Polyetherpolycarbonate is available from BASF under the tradenamepolytetrahydrofuran 1000 CD and 2000 CD.

[0039] A block polyoxyalkylene polymer also can be used in the reaction.For example, a propylene oxide terminated block of ethylene glycolmanufactured by BASF under the tradename PLURONIC R and an ethyleneoxide terminated block of propylene glycol manufactured by BASF underthe tradename of PLURONIC can be used for the polyoxyalkylene in thereaction. Examples of the block copolymers of the sequential addition ofethylene oxide and propylene oxide to ethylene diamine are made by BASFunder the tradename of PLURONIC, such as PLURONIC F68, F64, F127, L35;L92, L82, 17R2, and 25R2.

[0040] Preferably, the polyoxyalkylene diol used in forming thehydrophilic polyurethane resin is polyoxyethylene diol. The blends ofpolyoxyalkylene diols contain at least about 10% polyoxyethylene diol,preferably, at least about 20% polyoxyethylene diol, and most preferablyat least about 25% polyoxyethylene diol, by weight.

[0041] The amount of polyoxyalkylene diol having a molecular weight of400 to 20,000 in the polyurethane resin can vary from about 10% to about90%, preferably about 30% to about 90%, and most preferably about 40% toabout 90%, by weight, and the number average molecular weight (M_(n)) ofthe polyoxyalkylene diol can vary from about 400 to about 20,000,preferably from about 800 to about 15,000, and more preferably fromabout 1000 to about 12,000.

[0042] The alkylene qlycols can be purchased from numerous sources. Forexample, propylene glycol can be purchased from Aldrich Chemical Companyas 1,2-propanediol. The amount of the alkylene glycol (hard segment)component in the polyurethane resin can be about 0.01% to about 20%,preferably about 0.05% to about 15%, more preferably about 0.1% to about12%, still more preferably about 0.5% to about 10%, and most preferablyabout 1% to about 8%, by weight of the reaction mixture.

[0043] The diisocyanate in the reaction mixture can be an aliphaticdiisocyanate, an aromatic diisocyanate, or a mixture thereof. Thealiphatic diisocyanates are preferred. An especially preferreddiisocyanate is methylene bis (cyclohexyl-1-4isocyanate). Other examplesof diisocyanates are trimethylhexamethylene diisocyanate and isophoronediisocyanate. Representative examples of the preferred aliphaticdiisocyanates include, but are not limited to, tetramethylenediisocyanate, hexamethylene diisocyanate, trimethylene diisocyanate,cyclohexyl-1,2-diisocyanate, and cyclohexl-1,4-diisocyanate. Examples ofaromatic diisocyanates include 2,4-toluene diisocyanate and 2,6-toluenediisocyanate. Also suitable are the isocyanate equivalents which formurethane linkages, exemplified by nitrile carbonates, such asadiponitrile carbonates of U.S. Pat. No. 4,810,543, incorporated hereinby reference. The amount of diisocyanate varies from about 3% to about80%, preferably from about 4% to about 70%, more preferably from about5% to about 60%, still more preferably from about 6% to about 55%, andmost preferably from about 6.5% to about 50%, by weight. Thepolyurethane resins are prepared by reacting the polyoxyalkylene diolswith the diisocyanates.

[0044] The amount of water in the reaction mixture is about 0.01% toabout 0.75%, and more preferably about 0.35% to about 0.55%, by weightof the reaction mixture.

[0045] The amount of 2, 2-di-(hydroxymethyl) alkanoic acid in thereaction mixture is about 0.1% to about 30%, preferably about 0.2% toabout 20%, more preferably about 0.3% to about 10%, still morepreferably about 0.4% to about 8%, and most preferably about 0.5% toabout 7.0%, by weight. Preferably the 2,2-di-(hydroxymethyl) alkanoicacid is dimethylolpropionic acid. The final reaction product has an acidvalue of at least about 0.2, preferably at least about 0.5, and morepreferably at least about 1.

[0046] The ratio of NCO to OH groups from the diol, alkylene glycol,amine and water (i.e., the R-value) in the reaction mixture is about 0.4to about 1.1, preferably about 0.4 to about 1, and most preferably about0.5 to about 0.98. The most preferred weight average molecular weight(M_(w)) of the carboxylated polyurethane resin is about 15,000 to about150,000, preferably about 20,000 to about 70,000, and more preferablyabout 30,000 to about 65,000. The sum of all ingredients, including thediols, glycols, water, and diisocyanate in the reaction mixture totals100% by weight.

[0047] An another embodiment, the hydrophilic polyurethane resincomprises a reaction product of: (a) a diet having a major portion of apolyoxyethylene diol having an M_(n) of 6,000 to 10,000, and a minorportion of a polyoxypropylene diol having an M_(n) of about 1,000 toabout 3,500, a polyoxyethylene diol having an M_(n) of about 600 toabout 2000, or a mixture thereof; (b) an alkylene glycol; (c) adiisocyanate; (d) water in an amount of about 0.01% to about 0.8% byweight, by weight of the reaction mixture; and (e) a2,2-di(hydroxymethyl)alkanoic acid, and an equivalent mole weight ratioof NCO to OH of the water, diol and glycol of about 0.5 to about 0.98.Preferably at least 45% of the polyoxyethylene glycol of M_(n) about8000, more preferably at least about 55%, still more preferably at leastabout 65%, and most preferably at least 75%, by weight, is used in thetotal reaction mixture. The amount of the lower molecular weightpolyoxyethylene diol having an M_(n) of about 600 to about 2,000 isabout 1% to about 15%, and preferably from about 2% to about 10%, byweight of the reaction mixture. Preferably, the alkylene glycol isdiethylene glycol, cyclohexanedimethanol, dipropylene glycol, or amixture thereof.

[0048] The 2,2-di-(hydroxymethyl)alkanoic acid preferably isdimethylolpropionic acid. The amount of dimethylolpropionic acid isabout 0.1% to about 30%, preferably about 0.2% to about 20%, morepreferably about 0.3% to about 10%, still more preferably about 0.4% toabout 8%, and most preferably about 0.5% to about 2.7%, by weight of thereaction mixture. The final product has an acid value of at least about0.2, and preferably at least about 1, mg KOH/g resin. To achieve thefull advantage of the invention, the carboxylated polyurethane resin hasan acid value of at least 7 mg KOH/g resin.

[0049] Alternatively, an amine can be used in place of a portion of thewater in the reaction mixture. An amount of about 0.15% to about 0.6%amine, based on diglycolamine, is used with about 0.06% to about 0.5% ofwater, more preferably about 0.1% to about 0.40% of water, and mostpreferably of about 0.15% to about 0.30% of water, by weight.

[0050] The carboxylated polyurethane resins of this embodiment areespecially useful in hair spray compositions because the polyurethaneresins are soluble in ethanol/water mixtures, and in dilute neutral tobasic aqueous solutions, to form low viscosity solutions. Solutions ofthe polyurethane resins also exhibit improved sprayability, improvedfeel of sprayed hair, low flaking and crust, and improved set retentionof the hair.

[0051] For hair spray compositions, the hydrophilicity of thepolyurethane resin is an unexpected important property in combinationwith other desirable properties, such as washability. Conventional hairfixative resins are hydrophobic materials that impart a stiff feel tohair. The present polyurethane resins are hydrophilic, which gives thehair a soft, natural feel, yet are adhesive to the hair and impartexcellent hair set retention. It also has been found that the hairstyling properties of the polyurethane resin can be affected by smallchanges in the amount of water, the ratio of NCO/OH, and the amount ofthe di(hydroxymethyl)alkanoic acid in the reaction mixture.

[0052] For hair spray compositions, the preferred diol is apolyoxyethylene diol, preferably a polyoxyethylene diol of M_(n) about6000 to about 10,000, alternatively with about 1% to about 10% by weightof a polyoxyethylene diol of M_(n) about 1000 to 2500. The preferredwater level is about 0.01% to about 0.65%, preferably about 0.02% toabout 0.60%, more preferably about 0.05% to about 0.55%, and mostpreferably about 0.10% to about 0.50%, by weight.

[0053] Further, it has unexpectedly been found that the weight averagemolecular weight of these polymers can be decreased or increased by upto about 20,000 by modifying the amount of water in the reaction mixturewithin a predetermined range. The above-described carboxylatedpolyurethane resins preferably have an M_(w) of the reaction product ofabout 15,000 to about 100,000, and preferably about 20,000 to about55,000; and a kinematic viscosity at 3 wt. % in 55/42 ethanol/water (byweight) of about 4 to about 40 centistokes (cs) , formed from a range ofwater of about 0.1% to about 0.3% by weight of the reaction mixture, aNCO/OH ratio (i.e., R-value) of about 0.75 to about 0.95, and a range ofdimethylolpropionic acid of about 0.5% to about 2.7% by weight of thereaction mixture.

[0054] A polyurethane resin having an M_(w) of less than about 25,000can be formed using a water level of about 0.25% to about 0.40% byweight of the reaction mixture, a ratio of NCO/OH about 0.60 to about0.75, and a range of dimethylolpropionic acid of about 3.0% to about6.5% by weight of the reaction mixture. The polyurethane resin has akinematic viscosity at 3 wt. % in a 55/42 ethanol/water solution (byweight) of about 1 to about 10 cs. These polyurethane resins are usefulas hair styling aids and forming low viscosity solutions in hair stylingmedia. A polyurethane resin having an M_(w) of about 55,000 to about150,000 and a kinematic viscosity at 3 wt. % in 55/42 ethanol/water (byweight) of about 10 to about 60 cs can be formed using a range of waterabout 0.3% to about 0.45%, a preferred NCO/OH ratio of about 0.75 toabout 0.98, and a range of dimethylolpropionic acid of about 0.5% toabout 2.7%, by weight of the reaction mixture.

[0055] It also has been found that polyurethane resins prepared using anamount of water of about 0.08% to about 0.45% by weight in the reactionmixture, and a NCO/OH ratio of about 0.55 to about 0.95, preferably fromabout 0.6 to about 0.7, have a crust value of about 3 to about 5 and aset retention at 30 minutes and 75% relative humidity of about 80% toabout 90%. An amount of water of about 0.15% to about 0.45% by weight inthe reaction mixture and a NCO/OH ratio of about 0.6 to about 0.92,preferably from about 0.7 to about 0.9, can be used to providepolyurethane resins having a crust value of about 5 to about 9 and a setretention of about 85% to about 98% at 30 minutes and 75% relativehumidity.

[0056] Alternatively, small amounts of diglycolamine amine can besubstituted for water in the reaction mixture, e.g., about 0.02% toabout 1%, preferably about 0.03% to about 0.75%, more preferably about0.04% to about 0.5%, and most preferably 0.05% to about 0.4%diglycolamine, by weight, can be used in the reaction mixture.

[0057] The alkylene glycol used in this embodiment can be, for example,ethylene glycol, diethylene glycol, propylene glycol, dipropyleneglycol, cyclohexanediol, 1,4-butanediol, cyclohexanedimethanol,tripropylene glycol, or triethylene glycol; preferably diethyleneglycol, cyclohexanedimethanol, or dipropylene glycol; and mostpreferably diethylene glycol. The amount of the alkylene glycol (hardsegments) in the reaction mixture is about 0.01% to about 20%,preferably about 0.05% to about 15%, more preferably about 0.1% to about12%, still more preferably about 0.5% to about 10%, and most preferablyabout 1% to about 5%, by weight.

[0058] For hair spray compositions, the kinematic viscosity of asolution of the carboxylated polyurethane resin having a 55/42/3 weightratio of ethanol/water/polyurethane resin is less than about 1,000centistokes (e.g., about 1 to about 1,000 cs), preferably about 500 csor less, more preferably about 100 cs or less, still more preferablyless than about 80 cs, and most preferably less than about 60 cs.

[0059] In each embodiment, the polyurethane-forming reaction iscatalyzed by known catalysts. Tin-containing catalysts, such as tinsalts or organotin esters, for example, stannous octoate and dibutyltindilaurate, or tertiary amines, such as triethylene diamine andN,N,N′,N′-tetramethyl-1,3-butane diamine, are preferred. The catalyst isused in an amount effective to catalyze the reaction, i.e., about 0.001to 1 weight percent of the total weight of the reaction mixture.Reaction temperature is about 40° C. to about 120° C.

[0060] In addition to the carboxylated polyurethane resin, the hairspray composition contains 0% to about 80%, by total weight of thecomposition, of an alcohol. Preferably, the composition contains 0% toabout 55%, by weight, of an alcohol. In order to reduce the adverseenvironmental affects attributed to volatile organic compounds, theamount of alcohol is maintained at as low a level as possible withoutadversely affecting the esthetics or efficacy of the hair spraycomposition.

[0061] The alcohol typically used in the hair spray composition isethanol, although isopropyl alcohol also can be incorporated into thecomposition. The carboxylated polyurethane resins are readilysolubilized in a wide range of hydroalcoholic solutions, without theaddition of basic neutralizer, thereby permitting a decrease in theamount of alcohol present in the hair spray composition.

[0062] The hair spray composition also contains 15% to about 95%, bytotal weight of the composition, of water. The amount of water ismaximized in order to reduce the amount of VOC in the composition.Because the carboxylated polyurethane resins are hydrophilic, it is notnecessary to include a base in the water to neutralize and solubilizethe polyurethane resin.

[0063] Optional ingredients also can be incorporated into the hair spraycomposition. The identity of the optional ingredients is not limited aslong as the optional ingredients do not adversely affect the estheticsor efficacy of the hair spray composition. For example, a hair spraycomposition containing only a polyurethane resin, water, and alcohol canbe applied as a nonaerosol pump spray. The composition can be modifiedfor application as an aerosol spray by incorporating about 5% to about30%, by weight of the composition, of a propellant. The carboxylatedpolyurethane resin tolerates the propellant cases commonly used inaerosol compositions, such as the alkanes and carbon dioxide.

[0064] The optional propellant was included in the hair spraycompositions can be any liquefiable gas conventionally used for aerosolproducts. Examples of compounds that are suitable for use as propellantsare trichlorofluoromethane, dichlorodifluoromethane,dichlorotetrafluoroethane, monochlorodifluoromethane,trichlorotrifluoroethane, dimethyl ether, propane, n-butane, andisobutane, either singly or admixed. Water-soluble gases such asdimethyl ether, carbon dioxide, and/or nitrous oxide also can be used toobtain aerosol sprays having reduced flammability.

[0065] Water-immiscible, liquified, hydrocarbon and halogenatedhydrocarbon gases such as propane, butane, and chlorofluorocarbons canbe used advantageously to deliver the contents of an aerosol containerwithout the dramatic pressure drops associated with other immisciblegases. The head space left inside the aerosol container is not a factorbecause the liquified gas sits on top of the aqueous composition and thepressure inside the container is maintained at the vapor pressure of thesaturated hydrocarbon vapor.

[0066] Other insoluble, compressed gases such as nitrogen, helium, andfully fluorinated oxetanes and oxepanes also are useful to deliver thecompositions from aerosol containers. If the propellant, such asdimethyl ether, incorporates a vapor pressure suppressant (e.g.,trichloroethane or dichloromethane), the amount of suppressant isincluded as part: of the propellant for weight percentage calculations.

[0067] The hair spray compositions also can contain a variety of othernonessential, optional components. Such conventional optionalingredients are well known to those skilled in the art, e.g.,emulsifiers, such as anionic or nonionic surfactants; preservatives,such as benzyl alcohol, methyl paraben, propyl paraben, orimidazolidinylurea; cationic conditioners, such as cetyl trimethylammonium chloride, stearyl dimethyl benzyl ammonium chloride, anddi(partially hydrogenated tallow) dimethyl ammonium chloride; coloringagents, such as any of the FD&C or D&C dyes; perfume oils; and chelatingagents, such as ethylene-diaminetetraacetic acid. These optionalcomponents generally are included individually at a level of 0% to about5%, by weight of the total composition.

[0068] The aqueous formulations of the present invention also cancontain conventional hair spray adjuvants in amounts which generallyrange from 0% to about 2%, by weight, and preferably 0% to about 1%, byweight. Among the additives which can be used are plasticizers such asglycols, phthalate esters, and glycerine, silicones, emollients,lubricants, and penetrants, such as various lanolin compounds, proteinhydrolysates and other protein derivatives, ethylene adducts andpolyoxyethylene cholesterol.

[0069] The hair spray compositions of the present invention are preparedby simply admixing and dissolving the carboxylated polyurethane resinand any optional ingredients into an aqueous or hydroalcoholic carrier.The resulting solution can be used in a pump spray, or can bepressurized by the addition of an aerosol propellant in accordance withmethods well known in the art.

POLYMER PREPARATION POLYURETHANE RESIN A

[0070] Polyoxyethylene diol having a number average molecular weight(M_(n)) of 8000 was heated under vacuum to 0.20% so water, and 744 partsof the dried diol was added to 20.8 parts of diethylene glycol, 18.6parts of dimethyl propionic acid, and 5.51 parts of water. The mixturewas heated with stirring until a homogeneous melt was obtained. Then,135 parts of methylene bis-cyclohexyl-4-4′-diisocyanate were addedduring which the temperature decreased. The NCO/OH ratio (i.e., theR-value) was 0.50. When the temperature reached about 60° C., 2.25 ml ofdibutyltin dilaurate was added, and the mass was allowed to exotherm toabout 65° C. The mass was placed in an oven and held at 100° C. for 1.5hours to complete formation of the polyurethane resin. At aconcentration of 5 wt. %, the polyurethane resin dissolved in a 55/45ethanol/water (wt/wt) solution to give a milky solution having aviscosity of 11 centipoise (cps). Upon addition of dilute ammonia, theviscosity did not change and the solution became clear.

POLYURETHANE RESIN B

[0071] Polyoxyethylene diol having an M_(n) of 8000 was heated undervacuum to 0.053% of water, and 473 parts of the dried diol was added to13.2 parts of diethylene glycol, 11.5 parts of dimethylolpropionic acid,and C.12 part of water. The mixture was heated with stirring until ahomogeneous melt was obtained. Then, 69.7 parts of methylenebis-cyclohexyl-4-4′-diisocyanate were added during which the temperaturedecreased. The NCO/OH ratio was 0.90. When the temperature reached about64° C., 0.75 ml of dibutyltin dilaurate was added. The mass was held at100° C. for about one hour.

[0072] At 5 wt. % concentration, the polyurethane resin dissolved in5/45 ethanol/water (wt/wt) solution to give a milky solution having aviscosity of 12 cps. At 5% concentration in 30/65 ethanol/water (wt/wt),the viscosity was 34 cps. Upon addition of dilute ammonia, the viscosityof the former solution was 13 cps, and the viscosity of the lattersolution was 16 cps.

POLYURETHANE RESIN C

[0073] Polyoxyethylene dido having an M_(n) of 8000 was heated undervacuum to 0.030% of water, and 744 parts of the dried diol was added to20.8 parts of diethylene glycol, 18.6 parts of dimethylolpropionic acid,and 0.078 part of water. The mixture was heated with stirring until ahomogeneous melt was obtained. Then, 60 parts of methylenebis-cyclohexyl-4-4′-diisocyanate were added. The NCO/OH ratio was 0.50.When the temperature reached about 75° C., 2.25 ml of dibutyltindilaurate was added, and the mass was allowed to exotherm. The mass washeated at 100° C. for 1.5 hours. The polyurethane resin was dissolved inwater at 2 wt. % concentration to produce a solution with 4 cpsviscosity.

[0074] At 5 wt. % concentration, the polyurethane resin dissolved in55/45 ethanol/water (wt/wt) to give a slightly hazy solution having aviscosity of 9 cps. Upon addition of dilute ammonia, the solution had aviscosity of 7.5 cps, and became clear.

POLYURETHANE RESIN D

[0075] Polyoxyethylene diol having an M_(n) of 8000 was heated undervacuum to 0.0385% of water, and 744 parts of the dried diol was added to20.8 parts of diethylene glycol, 18.6 parts of dimethylolpropionic acid,and 0.01 part of water. The mixture was heated with stirring until ahomogeneous melt was obtained. Then, 100 parts of methylenebis-cyclohexyl-4-4′-diisocyanate were added. The NCO/OF ratio was 0.85.When the temperature reached about 68° C., 2.25 ml of dibutyl tindilaurate was added and the mass exothermed. The mass was heated at 100°C. for 1.5 hours to complete formation of the polymer.

[0076] At 2 wt. % concentration of the polyurethane resin in water, theslightly hazy solution had a viscosity of 9 cps, and at 2.5 wt % it hadviscosity of 11.2 cps. At 5 wt. % concentration, the polyurethane resindissolved in 55/45 ethanol/water (wt/wt) to give a hazy solution havinga viscosity of 11 cps. At 5 wt. % concentration in 30/65 ethanol/water(wt/wt) the slightly hazy solution had a viscosity was 19 cps. Uponaddition of dilute ammonia to bring the pH to 9.0, the viscosity of theformer solution was 11.5 cps and that of the latter was 12.5 cps. Bothsolutions were clear.

POLYURETHANE RESIN E

[0077] Polyoxyethylene diol having an M_(n) of 8000 was heated undervacuum to 0.048% of water, and 744 parts of the dried diol was added to21 parts of diethylene glycol, 38 parts of dimethylolpropionic acid, and0.071 part of water. The mixture was heated with stirring until ahomogeneous melt was obtained.

[0078] Then, 132 parts of methylene bis-cyclohexyl-4-4′-diisocyanatewere added. The NCO/OH ratio was 0.85. When the temperature reachedabout 73° C., 2.25 ml of dibutyltin dilaurate was added. The mass washeated at 100° C. for 1.5 hours to complete formation of the polymer.

[0079] The polyurethane resin was dissolved at 2 wt. % concentration inwater, and the resulting solution had a viscosity of 9.5. At 2.5 wt. %concentration, the viscosity of the solution was 13.5 cps. Bothsolutions had a slight haze. At 5 wt. % concentration, the polyurethanedissolved in 55/45 ethanol/water (wt/wt) to give a viscosity of 10 cps.At 5 wt. % in 30/65 ethanol/water (wt/wt) the viscosity was 20 cps. Bothsolutions were hazy. Dilute ammonia was added to increase the pH to 9.The viscosity of the former solution was 10, and the viscosity of thelatter solution was 13 cps. Both solutions were clear.

POLYURETHANE RESIN F

[0080] Polyoxyethylene diol having an M_(n) of 8000 was heated undervacuum to 0.050% of water, and 474 parts of the dried diol was added to13 parts of diethylene glycol, 12 parts of dimethylolpropionic acid, and0.15 part of water. The mixture was heated with stirring until ahomogeneous melt was obtained. Then, 73 parts of methylenebis-cyclohexl-1-4-4′-diisocyanate were added. The NCO/OH ratio was 0.94.When the temperature reached about 61° C., 1.5 ml of dibutyltindilaurate was added. The mass was heated at 100° C. for about one hour.

[0081] The polyurethane resin was dissolved at 5 wt. % concentration in55/45 and 30/65 ethanol/water (wt/wt), giving viscosities of 12.0 and23.5 cps, respectively. When the pH was raised with dilute ammonia, theviscosities were 9 and 14.4 cps, respectively.

POLYURETHANE RESIN G

[0082] Polyoxyethylene diol having an M_(n) of 8000 was heated undervacuum to 0.088% of water, and 744 parts of the dried diol was added to21 parts of diethylene glycol, 4.3 parts of dimethylolpropionic acid,and 0.020 part of water. The mixture was heated with stirring until ahomogeneous melt was obtained. Then, 81 parts of methylenebis-cyclohexyl-4-4-diisocyanate were added. The NCO/OH ratio was 0.85 .When the temperature reached about 61° C., 2.25 ml of dibutyltindilaurate was added, and the mass was allowed to exotherm. The mass washeated at 100° C. for about one hour to complete formation of thepolymer. At a 5 wt. % concentration, the polyurethane resin dissolved in55/45 ethanol/water (wt/wt) to give a solution with a viscosity of 127cps, and 2 cc of dilute ammonia in 180 grams reduced the viscosity to 69cps. Both solutions had very small amounts of insolubles.

POLYURETHANE RESIN H

[0083] Polyoxyethylene diol having an M_(n) of 8000 was heated undervacuum to 0.037% of water, and 744 parts of the dried diol was added to21 parts of diethylene glycol, 19 parts of dimethylolpropionic acid, and0.023 part of water. The mixture was heated with stirring until ahomogeneous melt was obtained. Then, 115 parts of methylenebis-cyclohexyl)-4-4′-diisocyanate were added. The NCO/OH ratio was 0.98.When the temperature reached about 65° C., 2.25 ml of dibutyltindilaurate was added, and the mass was allowed to exotherm. The mass washeated at 100° C. for about one hour to complete the polymerization.

[0084] At 5 wt. % concentration, the polyurethane resin dissolved in55/45 ethanol/water (wt/wt) to live a clear solution with 5 pH and aviscosity of 1680 cps. Adding 2 cc dilute ammonia to 180 grams ofsolution reduced the viscosity of 225 cps. Both solutions were clear.Sodium bicarbonate also clarified the solution.

POLYURETHANE RESIN I

[0085] Polyoxyethylene diol having an M_(n) of 8000 was heated undervacuum to 0.208% of water, and 744 parts of the dried diol was added to21 parts of diethylene glycol, 19 parts of dimethylolpropionic acid, and2.90 part of water. The mixture was heated until a homogeneous melt wasobtained. Then, 106 parts of methylene bis-cyclohexyl-4-4′-diisocyanatewere added. The NCO/OH ratio was 0.50. When the temperature was about63° C., 2.25 ml of dibutyltin dilaurate was added. The mass was allowedto exotherm, and then heated at 100° C for 1.5 hours. At a concentrationof 5 wt. % in 55/45 ethanol/water (wt/wt), the polyurethane resinproduced a milky solution having a viscosity of 12.5 cps, and at 5 wt. %in 30/60 ethanol/water (wt/wt), the milky solution had a viscosity of15.0 cps. Both solutions became clear upon the addition of diluteammonia, with viscosities of 14 and 13 cps, and solutions of 2 wt. %an,, 2.5 wt. % polyurethane in water had viscosities of 4.5 and 7.0 cps,respectively.

POLYURETHANE RESIN J

[0086] Polyoxyethylene diol having an M_(n) of 8000 and polyoxyethylenediol having an average molecular weight of 1450 were heated undervacuum, to 0.107% of water, and 1105 parts of the dried diol was addedto 83 parts of ethylene glycol, 193 parts of dimethylolpropionic acid,and 1.485 part of water. The mixture was heated with stirring until ahomogeneous melt was obtained. Then, 888 parts of methylenebis-cyclohexyl-4-4′-diisocyanate were added. The NCO/OH ratio was 0.93.When the temperature reached about 59° C., 3.0 ml of stannous octoatewas added, and the mass was allowed to exotherm. The mass was heated at100° C. for about one hour to complete formation of the polymer. Thesolutions had viscosity of 4.5 and 7.0 cps. About 5 wt. % polyurethaneresin in 55/45 ethanol/water (wt/wt) gave a partial solution of polymer;particles were noted floating in the solvent. The solution had aviscosity of 12.5 cps. Upon addition of dilute ammonia, the viscositywas 14 cps and the solution was clear.

POLYURETHANE RESIN K

[0087] Polyoxyethylene diol having an M_(n) of 8000 was heated undervacuum to 0.271% of water, and 736 parts of the dried diol was added to21 parts of diethylene glycol, 38 parts of dimethylolpropionic acid, and0.271 part of water. The mixture was heated with stirring until ahomogeneous melt was obtained. Then, 145 parts of methylenebis-cyclohexyl-4-4′-diisocyanate were added. The NCO/OH ratio was 0.75.When the temperature reached about 59° C., 1.85 ml of dibutyltindilaurate was added, and the mass was allowed to exotherm. The mass washeated at 100° C. for about one hour to complete formation of thepolymer. At a concentration of 5 wt. %, the polyurethane resin formed amilky solution in 55/45 ethanol/water (wt/wt) having a viscosity of 9.0cps. The mixture was made basic with dilute ammonia to provide a waterclear solution having a viscosity of 15.3 cps. The polyurethane resinwas used as a hair styling aid.

POLYURETHANE RESIN L

[0088] Polyoxyethylene diol having an M_(n) of 8000 was heated undervacuum to 0.276% of water, and 736 parts of the dried diol was added to21 parts of diethylene glycol, 24 parts of dimethylolpropionic acid, and0.270 parts of water. The mixture was heated with stirring until ahomogeneous melt was obtained. Then, 124 parts of methylenebis-cyclohexyl-4-4′-diisocyanate were added. The NCO/OH ratio was 0.75.When the temperature reached about 56° C., 1.85 ml of dibutyltindilaurate was added, and the mass was allowed to exotherm. The mass washeated at 100° C. for about one hour to complete formation of thepolymer. The polyurethane resin formed a milky solution in 55/45ethanol/water (wt/wt) at a concentration of 5 wt. %. The pH was 5.0 andthe viscosity was 9.0 cps. The pH of about 20 cc of solution wasincreased to about 7 with dilute ammonia, potassium hydroxide, sodiumbicarbonate, and lithium acetate dihydrate. The slightly basic solutionswere water clear, and the viscosity of solution with ammonia was 15 cps.

POLYURETHANE RESIN M

[0089] Polyoxyethylene diol having an M_(n) of 1450 was heated undervacuum to a water level of 0.244% and the 227 parts of the dried diolwas added to 156 parts of polyoxyethylene diol having an M_(n) of 1000,94 parts of polyoxyethylene diol having an M_(n) of 600, 62 parts ofpolyoxyethylene diol having an M_(n) of 400, 120 parts of ethyleneglycol, 381 parts of polyoxytetramethylene glycol having an M_(n) of2000, 104 parts of polyoxypropylene glycol having an M_(n) of 1025, 93parts of dimethylolpropionic acid, and 4.51 parts of water. The mixturewas heated with stirring until a homogeneous melt was obtained. Then,1026 parts of methylene bis-cyclohexyl-4-4′-diisocyanate were added. TheNCO/OH ratio was 0.98. When the temperature reached about 50° C., 3.4 mlof stannous octoate (T₉) was added, and the mass was allowed toexotherm. The mass was heated at 100° C. for about one hour to completeformation of the polymer. The polyurethane resin had a tear strength of520 pounds per inch, and modulus at 100% elongation of 1470 pounds persquare inch compared to values of 260 pounds/inch and 670 pounds persquare inch for a similar polyurethane resin made withoutdimethylolpropionic acid. The polyurethane resin had a water content of21% and a linear expansion of 8% after exposure to water and similarpolyurethane resin without any dimethylolpropionic acid hadcorresponding values of 25% and 11%. The polyurethane resin wasdissolved in 75/25 tetrahydrofuran/ethanol to give a viscosity of 15cps. Upon the addition of 5 wt. % water, the viscosity increased to 6120cps.

POLYURETHANE RESIN N

[0090] Polyoxyethylene diol having an M_(n) of 8000 was heated undervacuum to 0.156% of water and 756 parts of the dried diol was added to21 parts of diethylene glycol, 39 parts of dimethylolpropionic acid, and0.25 part of water. The mixture was heated with stirring until ahomogeneous melt was obtained. Then, 136 parts of methylenebis-cyclohexl-4-4′-diisocyanate were added. The NCO/OH ratio was 0.75.When the temperature reached about 66° C., 1.85 ml of dibutyltindilaurate was added, and the mass was allowed to exotherm. The mass washeated at 100° C. for about one hour to complete formation of thepolymer. The polyurethane resin dissolved in a slightly basic 55/45ethanol/water solution (wt/wt) at a concentration of 5 wt. % to producea clear solution with a viscosity of 11 cps. The polyurethane resin wasused to make an excellent hair styling aid. The polyurethane resinimparted a crust rating of 6.9, a feel of 5.5, a set retention of 95% at30 minutes, and a set retention of 90% at 60 minutes to treated hair.

POLYURETHANE RESIN O

[0091] Polyoxyethylene diol having an M_(n) of 8000 was heated undervacuum to 0.032% of water and 736 parts of the dried diol was added to21 parts of diethylene glycol, 18 parts of dimethylolpropionic acid, and2.06 parts of water. The mixture was heated with stirring until ahomogeneous melt was obtained. Then, 113 parts of methylenebis-cyclohexl 4-4′-diisocyanate were added. The NCO/OH ratio was 0.75.When the temperature reached about 65° C., 1.85 ml of dibutyltindilaurate was added, and the mass was allowed to exotherm. The mass washeated at 100° C. for about one hour to complete formation of thepolymer. The polymer dissolved in a slightly basic 55/45 ethanol/watersolution (wt/wt) at a concentration of 5 wt. % to produce a clearsolution with a viscosity of 13 cps. The polyurethane resin had akinematic viscosity of 6.5 cs in 55/42/3 ethanol/water/polymer by weightsolution. The polyurethane resin was used to make an excellent hairstyling aid. The polyurethane resin imparted a crust rating of 4.2, afeel of 4.8, a flaking rating of 4.2, a set retention of 86% at 30minutes, and a set retention of 73% at 60 minutes to treated hair.

POLYURETHANE RESIN P

[0092] Polyoxyethylene diol having an M_(n) of 8000 was heated undervacuum to 0.060% of water and 736 parts of the dried diol was added to21 parts of diethylene glycol, 18 parts of dimethylolpropionic acid, and2.84 parts of water. The mixture was heated with stirring until ahomogeneous melt was obtained. Then, 139 parts of methylenebis-cyclohexyl-4-4′-diisocyanate were added. The NCO/OH ratio was 0.85.When the temperature reached about 64° C., 1.85 ml of dibutyltindilaurate was added, and the mass was allowed to exotherm. The mass washeated at 100° C. for about one hour to complete formation of thepolymer. The polyurethane resin had an M_(w) of 76,000 and dissolved ina slightly basic 55/45 ethanol/water solution (wt/wt) at a concentrationof 5 wt. % to give a viscosity of 18 cps. The polyurethane resin had akinematic viscosity of 14.7 cs in 55/42/3 ethanol/water/polymer solutionby weight. The polyurethane resin was used to make an excellent hairstyling aid.

[0093] The polyurethane resin imparted a crust rating of 8.3, a feel of9.6, a flaking rating of 8.4. a set retention of 94% at 30 minutes, anda set retention of 91% at 60 minutes to treated hair.

POLYURETHANE RESIN Q

[0094] Polyoxyethylene diol having an M_(n) of 8000 was heated undervacuum to 0.074% of water and 281 parts added to 7.9 parts of diethyleneglycol, 55 parts of dimethylolpropionic acid, and 1.38 parts of water.The mixture was heated with stirring until a homogeneous melt wasobtained. Then, 109 parts of methylene bis-cyclohexyl-4-4′-diisocyanatewere added.

[0095] The NCO/OH ratio was 0.65. When the temperature reached about 70°C., 0.68 ml of dibutyltin dilaurate was added, and the mass was allowedto exotherm. The mass was heated at 100° C. for about one hour tocomplete formation of the polymer. The polyurethane resin dissolved in aslightly basic 55/45 ethanol/water solution (wt/wt) at a concentrationof 5 wt. % to produce a clear solution with a viscosity of 10 cps.

POLYURETHANE RESIN R

[0096] Polyoxyethylene diol having an M_(n) of 8000 was heated undervacuum to 0.099% of water and 306 parts of the dried diol was added to34 parts of a block copolymer of ethylene oxide and propylene oxide madeby BASF under the tradename of F127, 9.5 parts of diethylene glycol, 27parts of dimethylolpropionic acid, and 1.30 parts of water. The mixturewas heated with stirring until a homogeneous melt was obtained. Then, 77parts of methylene bis-cyclohexyl-4-4′-diisocyanate were added. TheNCO/OH ratio was 0.65. When the temperature reached about 67° C., 0.68ml of dibutyltin dilaurate was added, and the mass was allowed toexotherm. The mass was heated at 100° C. for about one hour to completeformation of the polyurethane resin. The polyurethane resin can bedissolved in slightly basic 55/45 ethanol/water (wt/wt) at aconcentration of 5 wt. % to produce a clear solution with a viscosity ofless than 20 cps.

POLYURETHANE RESIN S

[0097] Polyoxyethylene diol having an M_(n) of 8000 was heated undervacuum to 0.072% of water, and 343 parts of the dried diol was added to18 parts of polyoxypropylene glycol of 425 molecular weight, 10 parts ofdiethylene glycol, 18 parts of dimethylolpropionic acid, and 0.43 partof water. The mixture was heated with stirring until a homogeneous meltwas obtained. Then, 79 parts of methylenebis-cyclohexyl-4-4′-diisocyanate were added. The NCO/OH ratio was 0.85.When the temperature reached about 58° C., 0.68 ml of dibutyltindilaurate was added, and the mass was allowed to exotherm. The mass washeated at 100° C. for about one hour to complete formation of thepolymer. The polyurethane resin dissolved in 55/45 ethanol/water (wt/wt)at a concentration of 5 wt. % to produce a clear solution with aviscosity of 12 cps.

POLYURETHANE RESIN T

[0098] Polyoxyethylene diol having an M_(n) of 8000 was heated undervacuum to 0.061% of water, and 736 parts of he dried diol was added to21 parts of diethylene glycol, 59 parts of dimethylolpropionic acid, and1.11 part of water. The mixture was heated with stirring until ahomogeneous melt was obtained. Then, 185 parts of methylenebis-cyclohexyl-4-4′-diisocyanate were added. The NCO/OH ratio was 0.85.When the temperature reached about 63° C., 1.8 ml of dibutyltindilaurate was added, and the mass was allowed to exotherm.. The mass washeated at 100° C. for about one hour to complete formation of thepolymer. The polyurethane resin had an M_(w) of 21,000 and dissolved inslightly basic 55/45 ethanol/water solution (wt/wt) at a concentrationof 5 wt. % was clear and had a viscosity of 10 cps. The polyurethaneresin had a kinematic viscosity of 6.15 cts in 55/42/3ethanol/water/polymer solution by weight. The polyurethane resin wasused as a hair styling aid, and imparted a crust rating of 6.3, a feelof 8.1, a flaking rating of 8.3, a set retention of 81% at 30 minutes,and a set retention of 68% at 60 minutes to treated hair.

POLYURETHANE RESIN U

[0099] Polyoxyethylene diol having an M_(n) of 8000 was heated undervacuum to 0.215% of water, and 736 parts of the dried diol was added to21 parts of diethylene glycol, 59 parts of dimethylolpropionic acid, and1.81 parts of water. The mixture was heated with stirring until ahomogeneous melt was obtained. Then, 168 parts of methylenebis-cyclohexyl-4-4′-diisocyanate were added. The NCO/OH ratio was 0.65.When the temperature reached about 70° C., 1.85 ml of dibutyltindilaurate was added, and the mass was allowed to exotherm. The mass washeated at 100° C. for about one hour to complete formation of thepolyurethane resin. The polyurethane resin had an M_(w) of 15,000 anddissolved in slightly basic 55/45 ethanol/water (wt/wt) solution at aconcentration of 5 wt. % was clear and had a viscosity of 10 cps. Thepolyurethane resin had a kinematic viscosity of 4.60 cps in 55/42/3ethanol/water/polymer solution by weight. The polyurethane resin can beused in a hair styling aid to impart superior soft feel, excellent setretention, low crust, and low flaking properties to treated hair. Thehair styling aid imparted a crust rating of 4.5, a feel of 4.5, aflaking rating of 1.8, and a set retention of 85% at 30 minutes totreated hair.

POLYURETIAE RESIN V

[0100] Polyoxyethylene diol having an M_(n) of 8000 was heated undervacuum to 0.060% of water, and 736 parts of the dried diol was added to21 parts of diethylene glycol, 18 parts of dimethylolpropionic acid, and0.96 part of water. The mixture was heated with stirring until ahomogeneous melt was obtained. Then, 114 parts of methylenebis-cyclohexyl-4-4′-diisocyanate were added. The NCO/OH ratio was 0.85.When the temperature reached about 63° C., 1.85 ml of dibutyltindilaurate was added, and the mass was allowed to exotherm. The mass washeated at 100° C. for about one hour to complete formation of thepolyurethane resin. The polyurethane resin dissolved in slightly basic55/45 ethanol/water solution (wt/wt) at a concentration of 5 wt. % wasclear and had a viscosity of 14 cps. The polyurethane resin had an M_(w)of 40,000 and can be used in a hair styling aid to impart a superiorsoft feel, excellent set retention, low crust, and low flakingproperties to hair. The hair styling aid imparted a crust rating of 4.9,a feel of 6.7, a flaking rating of 7, a set retention of 97% at 30minutes, and a set retention of 95% at 60 minutes to treated hair.

POLYURETHANE RESIN W

[0101] Polyoxyethylene diol having an M_(n) of 8000 was heated undervacuum to 0.060% of water, and 336 parts of the dried diol was added to9.3 parts of diethylene glycol, 27 parts of dimethylolpropionic acid,8.2 parts of diglycolamine and 0.002 part of water. The mixture washeated with stirring until a homogeneous melt was obtained. Then, 73parts of methylene bis-cyclohexyl-4-4′-diisocyanate were added. TheNCO/OH ratio was 0.65. When the temperature reached about 65° C., 0.92ml of dibutyltin dilaurate was added, and the mass was allowed toexotherm. The mass was heated at 100° C. for about one hour to completeformation of the polymer. The polyurethane resin dissolved in slightlybasic 55/45 ethanol/water solution (wt/wt) at a concentration of 5 wt. %was clear. The polyurethane resin had a kinematic viscosity of 5.93 csin 55/42/3 ethanol/water/polymer solution by weight.

POLYURETHANE RESIN X

[0102] Polyoxyethylene diol having an M_(n) of 8000 and polyoxyethylenediol having an M_(n) of 1450 were heated under vacuum to 0.132% ofwater, and 291 parts of the higher molecular weight dried diol and 15.3parts of lower molecular weight dried diol were added to 9.5 parts ofdipropylene glycol, 27 parts of dimethylolpropionic acid, 34 parts ofpolyoxypropylene glycol of 425 molecular weight, and 1.146 part ofwater. The mixture was heated with stirring until a homogeneous melt wasobtained. Then, 89 parts of methylene bis-cyclohexyl-4-4′-diisocyanatewere added. The NCO/OH ratio was 0.65. When the temperature reachedabout 67° C., 0.68 ml of dibutyltin dilaurate was added, and the masswas allowed to exotherm. The mass was heated at 100° C. for about onehour to complete formation of the polymer. The polyurethane resindissolved in slightly basic 55/45 ethanol/water solution (wt/wt) at aconcentration of 5 wt. % was clear, and had a viscosity of 8 cps. Thepolyurethane resin can be used in a hair spray composition to givetreated hair a superior soft feel, excellent set retention, low crust,and low flaking properties.

POLYURETHANE RESIN Y

[0103] A batch of 13,147 parts of polyoxyethylene diol having an M_(n)of 8000 was added to a five-gallon electrically heated reactor andheated under vacuum to dry the glycol. The dried diol was added to 368parts of diethylene glycol and 321 parts of dimethylolpropionic acid,and the mixture was heated to 105° C. in order to melt the ingredients.The mixture was allowed to cool to about 175° F. to about 185° F. andthe water level was analyzed by Karl Fisher method as 0.0675%. Then,19.41 grams of water was added to the mixture to bring the total waterto 28.75 grams of water.

[0104] A separate reactor contained 2073 parts of methylenebis(cyclohexyl-4-isocyanate). To the diols was added 33.04 cc ofdibutyltin dilaurate. Then the isocyanate was heated to about 110°-115°F., and both Liquids were forced out under nitrogen pressure using apiston cylinder at about a ratio of 0.1492. Twelve shots of liquid werepumped into a polypropylene tub and heated for one hour at 100° C. TheNCO/OH ratio was 0.85.

[0105] The polyurethane resin was dissolved at 3 wt. % solids in 55/45ethanol/water solution (wt/wt) and gave viscosities of 11 cps using aBrookfield viscometer. The polyurethane resin had a kinematic viscosityof 7.67 cs in 55/42/3 ethanol/water/polymer solution by weight. Thepolymer had an M_(w) of 40,000.

[0106] The polyurethane resin was used in a hair spray to give hair asuperior soft feel, excellent set retention, low crust, and low flakingproperties.

POLYURETHANE RESIN Z

[0107] A batch of 13,147 parts of polyoxyethylene diol having an M_(n)of 8000 was added to a five-gallon electrically heated reactor andheated under vacuum to dry the glycol. The dried diol was added to 368parts of diethylene glycol and 321 parts of dimethylolpropionic acid,and the mixture was heated to 105° C. in order to melt the ingredients.The mixture was allowed to cool to about 175° F. to about 185° F. and asample of the mixture was taken and analyzed for its water content byKarl Fisher method. The mixture had a water content of 0.0625% water and26.66 grams of water was added to the mixture to bring the total waterto 35.31 grams of water.

[0108] A separate reactor contained 2162 parts of methylenebis(cyclohexyl-4-isocyanate). To the diols was added 33.04 cc dibutyltindilaurate. Then the diisocyanate was heated to about 110°-115° F., andboth liquids were forced out under nitrogen pressure using a pistoncylinder at about a ratio of 0.1555. Twelve shots of liquid were pumpedinto a polypropylene tub and heated for one hour at 100° C. The NCO/C)Hratio was 0.85.

[0109] The polyurethane resin was dissolved at 3% solids in 55/45ethanol/water solution (wt/wt) and gave a viscosity of 11.5 cps using aBrookfield viscometer. The polyurethane resin had a kinematic viscosityof 9.81 cs in 55/42/2 ethanol/water/polymer solution by weight, and anM_(w) of 49,000.

POLYURETHANE RESIN AA

[0110] Polyoxyethylene diol having an M_(n) of 8000 was heated undervacuum to 0.028% of water, and 736 parts of the dried diol was added to21 parts of cyclohexanedimethanol, 18 parts of dimethylolpropionic acid,and 1.21 parts of water. The mixture was heated with stirring until ahomogeneous melt was obtained.

[0111] Then, 102 parts of methylene bis-cyclohexyl-4-4′-diisocyanatewere added. The NCO/OH ratio was 0.85. When the temperature reachedabout 65° C., 1.85 ml of dibutyltin dilaurate was added, and the masswas allowed to exotherm. The mass was heated at 100° C. for about onehour to complete formation of the polyurethane resin. The polyurethaneresin can be dissolved in slightly basic 55/45 ethanol/water solution(wt/wt) at a concentration of 5 wt. % to give a low viscosity clearsolution. The polyurethane resin was used in a hair spray composition togive treated hair a superior soft feel, excellent set retention, lowcrust, and low flaking properties.

POLYURETHANE RESIN BB

[0112] A polyoxyethylene diol having an M_(n) of 8000 was heated undervacuum to 0.048% of water, then 744 parts of the dried diol was added to21 parts diethylene glycol, 4.3 parts dimethylolpropionic acid, and 0.37parts water. The resulting mixture was heated, with stirring, until ahomogeneous melt was obtained. Then, 88 parts methylenebis-cyclohexyl-4-4 ′-diisocyanate was added to the mixture. The NCO/OHratio was about 0.98. When the temperature reached about 65° C., 2.25 mlof dibutyl tin dilaurate was added to the mixture, and the massexothermed. The mass then was heated to 100° C., and held at 100° C. forabout one hour to complete polyurethane formation. The polyurethaneresin had an M_(w) of 141,000. At 5% concentration, the polyurethaneresin dissolved in 55/45 ethanol water to give a solution having aviscosity of 180 cps. At a concentration of 3%, in 60/40 propyleneglycol/water, the solution had a viscosity of 5300 cps. A gel containing19% of the polyurethane resin in 20/80 propylene glycol/water was tough,exceptionally clear, and adhered to glass. The viscosity of the gel wasreduced by raising the pH about 7.0.

POLYURETHANE RESIN CC

[0113] A polyoxyethylene diol having an M_(n) of 8000 was heated undervacuum to 0.037% of water, then 744 parts of the dried diol was added to21 parts diethylene glycol, 18.6 parts dimethylolpropionic acid, and0.23 parts water. The resulting mixture was heated, with stirring, untila homogeneous melt was obtained. Then, 115 parts methylenebis-cyclohexyl-4-4′-diisocyanate was added to the mixture. The NCO/OHratio was about 0.98. When the temperature reached about 65° C., 2.25 mldibutyl tin dilaurate was added to the mixture, and the mass exothermed.The mass then was heated to 100° C., and held at 100° C. for about onehour to complete polyurethane formation. The polyurethane resin had anM_(w) of 63,000. At 5% concentration, the polyurethane resin dissolvedin 55/45 ethanol water to give a solution having a viscosity of 1680cps, and a reduced viscosity of 225 cps upon the addition of 2 mlammonia to 180 grams of the solution. At a concentration of 3%, in 60/40propylene glycol/water, the solution had a viscosity of 144 cps. A gelcontaining 19% of polymer in 20/80 propylene glycol/water was tough,exceptionally clear, and adhered to glass, displaying improved adhesiveproperties compared to gels made using a polyurethane without thealkanoic acid.

POLYURETHANE RESIN DD

[0114] A polyoxyethylene diol having an M_(n) of 8000 was heated undervacuum to 0.062% of water, then 470 parts of the dried diol was added to13.2 parts diethylene glycol, 11.4 parts dimethyl prooionic acid, and0.55 parts water. The resulting mixture was heated, with stirring, untila homogeneous melt was obtained. Then, 76 parts methylenebis-cyclohexyl-4-4′-diisocyanate was added to the mixture. The NCO/OHratio was about 0.90. When the temperature reached about 61° C., 1.44 mldibutyl tin dilaurate was added to the mixture, and the mass exothermed.The mass was heated to 100° C., and held at 100° C., for about one hourto complete formation of the polyurethane. The polyurethane resin had anM_(w) of 46,000. At a 5 % concentration, the polyurethane dissolved in55/45 ethanol water to give a solution having a viscosity of 13 cps, anda reduced viscosity of 12 cps upon the addition of 2 ml ammonia to 180grams of the solution. At a concentration of 3%, in 60/40 propyleneglycol/water, the solution had a viscosity of 64 cps. At a concentrationof 5%, in 30/70 ethanol/water, the solution had a viscosity of 34 cps,and upon neutralization, the viscosity dropped to 16 cps. A gel madewith 19% of polyurethane in 20/80 propylene glycol/water was tough,exceptionally clear, and adhered to glass, displaying improved adhesiveproperties compared to gels made using polymer without the alkanoicacid.

[0115] An important property of a hair spray composition is the abilityto wash the hair setting resin from the hair, and thereby avoid polymerbuildup on the hair. In accordance with an important feature of thepresent invention, the carboxylated polyurethane resin used in the hairspray composition can be removed from the hair by simply shampooing thehair. The unexpected washability of the hair spray composition isattributed to the hydrophilic nature of the polyurethane resin, andespecially to the acid value of the carboxylated polyurethane resin.When the acid value of the carboxylated polyurethane resin is at leastabout 7 mg KOH/g of resin, e.g., about 7 to about 50 mg KOH/g of resin,the polyurethane resin can be rinsed from the hair during shampooingwithout the need to neutralize the resin with an organic base.

[0116] The acid value is an indication of the number pendant carboxylicacid groups on the polyurethane resin backbone. Although noncarboxylatedpolyurethane resins are hydrophilic, they are difficult to wash from thehair in a short time. Washability is enhanced by incorporating pendantcarboxylic acid groups onto the polyurethane backbone.

[0117] The effect of acid value is illustrated in Tables 1 and 2,wherein it is shown that washability is independent of M_(w) or R-value,but varies with acid value. In effect, carboxylated polyurethane resinshaving an acid value of at least about 7 mg KOH/g of resin or greater,i.e., about 7 to about 50 mg KOH/g resin, had improved washability overresins having an acid value less than 7 mg KOH/g resin. TABLE 1PROPERTIES OF POLYURETHANE RESINS (R-VALUE = 0.73 TO 0.98) Poly-urethane R- Molecular Wash- Resin value Water Acid Value¹ Weight² PDI³ability⁴ 1 0.98 low 0.42 174,000 2.00 no  2¹⁶ 0.98 low 2.28 141,000 2.00no 3 0.84 low 8.01 28,000 2.00 yes 4 0.93 low 7.88 37,000 2.00 yes 50.98 low 8.28 63,000 2.00 yes 6 0.98 medium 0.50 188,000 2.20 no 7 0.85medium 2.47 64,000 1.90 no 8 0.85 medium 8.62 37,000 1.70 yes 9 0.88medium 7.87 30,000 1.60 yes 10  0.90 medium 7.70 43,000 1.80 yes 11 0.90 medium 8.04 39,000 1.70 yes 12  0.94 medium 7.78 39,000 1.80 yes13  0.85 high 7.91 38,000 1.80 yes 14  0.90 high 7.70 46,000 1.90 yes15  0.73 low 15.19 23,000 na yes 16  0.73 low 7.10 59,000 na yes 17 0.98 low 3.66 117,000 na no 18  0.98 low 4.03 85.000 na no

[0118] TABLE 2 PROPERTIES OF POLYURETHANE RESINS (R-VALUE = 0.65 TO0.85) Poly- urethane R- Acid Molecular Wash- Resin value Water Value¹Weight² ability⁴ 19 0.75 med 16.30 18,000 yes  20⁵ 0.65 high 8.22 26,000yes 21 0.65 med 17.02 16,000 yes  22⁶ 0.85 low 23.31 21,000 yes  23⁷0.75 high 22.48 24,000 yes  24⁸ 0.85 high 7.75 76,000 yes 25 0.75 high16.53 20,000 yes  26⁹ 0.65 high 24.22 15,000 yes 27 0.85 med 16.3727,000 yes 28 0.75 low 16.45 25,000 yes  29¹⁰ 0.75 med 8.11 35,000 yes 30¹¹ 0.85 low 8.01 40,000 yes

[0119] A hair spray composition of the present invention also can beevenly delivered as a spray. In particular, the carboxylatedpolyurethane resins are suitable for preparing hair spray compositionscontaining various levels of volatile organic compounds (VOC). Hairspray compositions containing 55% VOC and having good spray propertieshave a viscosity of about 1 to about 10 cps. Hair spray compositionscontaining 80% VOC and having good spray properties have a viscosity ofabout 1 to about 25 cps. Accordingly, it was found that to provide ahair spray composition having excellent spray characteristics, the M_(w)of the carboxylated polyurethane resin is about 15,000 to about 70,000,and preferably about 20,000 to about 65,000.

[0120] Aerosol and nonaerosol hair spray compositions of the presentinvention were prepared by dissolving 5%, by weight, of a carboxylatedpolyurethane resin in a blend of water and ethanol, then pouring theresulting solution into an aerosol can. The filled can was crimped witha conventional aerosol valve. Then 30 weight % dimethyl ether (i.e.,DME), was charged into the aerosol can. The nonaerosol, pump hair spraycompositions were prepared by simply dissolving the polyurethane resinin a water/ethanol blend. The composition of the examples set forth inTables 3 and 4 are summarized below: Aerosol Hair Spray (55% VOC)Polyurethane resin  5 (% wt.) Ethanol 25 DME 30 Water 40 Aerosol HairSpray (80% VOC) Polyurethane resin  5 (% wt.) Ethanol 50 DME 30 Water 15Pump Hair Spray (80% VOC) Polyurethane resin  5 (% wt.) Ethanol 80 Water15 Pump Hair Spray (55% VOC) a b Polyurethane resin  5 (% wt.)  3 (%wt.) Ethanol 55 55 Water 40 42

[0121] The results summarized in Tables 3 and 4 show that the presenthair spray compositions containing a carboxylated polyurethane resin canbe applied to the hair as an aerosol spray or a pump spray. The resultsalso illustrate that sprayability of the hair spray composition isoptimized when the polyurethane resin has an M_(w) of about 15,000 toabout 70,000. TABLE 3 SPRAYING PROPERTIES OF HAIR SPRAY COMPOSITIONSCONTAINING 5% WT/WT OF A POLYURETHANE RESIN Viscosity [mm²/S]¹² AerosolSpray Pattern¹³ Pump Spray Pattern¹⁴ Polyurethane Resin 55% VOC 80% VOC55% VOC 80% VOC 55% VOC 80% VOC 1 860.00 v. viscous v. bad v. bad badbad  2¹⁶ 180.00 v. viscous v. bad v. bad v. bad bad 3 8.50 7.15 goodgood good good 4 9.80 9.3 marginal good good good 5 24.56 16.03 bad badmarginal marginal 6 930.00 v. viscous v. bad v. bad bad bad 7 21.3513.32 v. bad bad marginal marginal 8 13.40 9.51 marginal good good good9 10.30 7.83 marginal good good good 10  14.68 11.05 bad good good good11  13.20 9.41 bad good good good 12  12.55 9.33 bad good good good 13 12.79 10.03 bad good good good 14  17.06 7.9 bad good good good 15  8.33na¹⁵ good na good na 16  20.37 na marginal na marginal na 17  91.51 nabad na bad na 18  27.77 na bad na marginal na # the spray particles aretoo large or coarse (i.e., particle average diameter greater than 200microns), the composition foams or clogs the actuator, or the spraycross section is narrow (i.e., less than 2 inches diameter). A marginalspray pattern is somewhat coarse, having an average particle diameterbetween 100 to 150 microns. A good spray pattern is when the # sprayleaves the can smoothly without sputtering or clogging, the sprayparticle size is fine, the particle average diameter is less than 100microns, and there is no foaming;

[0122] TABLE 4 HAIR SPRAY COMPOSITIONS (55% WT. ETHANOL) 3% PolyurethaneResin 5% Polyurethane Resin Polyurethane Viscosity Pump Spray ViscosityPump Spray Resin [mm²/s]¹² Pattern¹⁴ [mm²/s] Pattern 19  5.03 good  7.73good 20⁵  5.84 good  9.95 good 21  4.28 good  7.47 good 22⁶  6.15 good10.03 marginal 23⁷  5.92 good 10.79 marginal 24⁸ 14.71 marginal 14.71marginal 25  5.69 good  9.25 good 26¹⁰ 15.00 good  7.05 good 27 27.00good 12.47 marginal 28 25.00 good 10.58 marginal 29¹⁰ 35.00 good 10.85marginal 30¹¹ 40.00 marginal 13.15 marginal Control¹⁷ 10.90 good 16.51bad

[0123] The hair spray compositions also impart good hold and hair setretention to treated hair. For example, a hair spray compositioncontaining a carboxylated polyurethane resin having an M_(w) of about30,000 or greater provided equal or better set retention at 70% relativehumidity than a control hair spray product containing the resinAMPHOMER. At 85% relative humidity, a hair spray composition containinga polyurethane resin having an M_(w) of about 20,000 or greater providedequal or better set retention than a control hair spray productcontaining AMPHOMER. AMPHOMER is an acrylic copolymer resin and iswidely used resin in commercial hair spray products. Hair spray productscontaining AMPHOMER, therefore, are used as a control for comparison tohair spray compositions containing a carboxylated polyurethane resin.

[0124] In tests designed to test the ability of a present hair spraycomposition to hold the hair, hair spray compositions containing 3 partsby weight carboxylated polyurethane resin dissolved in a mixture of 55parts by weight ethanol and 42 parts by weight water were prepared.Because sprayability of the composition is optimized when the M_(w) ofthe polyurethane resin is about 70,000 or less, polyurethane resinshaving an M_(w) of about 65,000 or greater were not used in these tests.The polyurethane resins and the test results are summarized in Table 5.Each polyurethane resin used in these tests had an acid value of atleast 7 mg KOH/g resin, and typically about 7.5 to about 50 mg KOH/gresin. TABLE 5 Polyurethane R-Value Molecular % Static Set Retention 1hr. Crust Example Resin [NCO/OH] Weight (M_(w)) @ 70% R.H. (95% C.L.)¹⁸[gram-force] Washability 1 3 0.84 28,000 71.00(=) 133(≠) yes 2 4 0.9337,000 82.50(≠) 244(≠) yes 3 5 0.98 63,000 86.71(≠) 267(≠) yes 4 8 0.8537,000 81.00(≠) 188(≠) yes 5 9 0.88 30,000 66.50(≠) 155(≠) yes 6 10 0.9043,000 83.24(≠) 297(=) yes 7 11 0.90 39,000 86.06(≠) 235(≠) yes 8 120.94 39,000 83.00(=) 226(≠) yes 9 13 0.85 38,000 79.50(=) 232(≠) yes 1014 0.90 46,000 86.30(≠) 296(≠) yes Control¹⁷ — — 76.00 331 yes

[0125] The set retention test measures the ability of a hair spraycomposition to hold or retain a hair style for an extended time at aparticular relative humidity. Set retention was measured by applying 0.5cc (cubic centimeters) of the hair spray composition to a one gram hairtress, and testing six tresses per composition. The sprayed tresses wereallowed to dry overnight, at 30% relative humidity (i.e., RH), in azigzag shape. The tresses were hung inside a humidity chamber at 25° C.and a predetermined relative humidity (e.g., 70% RH). The relaxed lengthwas recorded of the tresses and set retention was calculated using theequation:${{\% \quad {Set}\quad {Retention}} = {\frac{L - L_{t}}{L - L_{o}} \times 100}},$

[0126] wherein L is the length of the fully extended tress, L_(o) is thelength of sprayed hair before relaxation, L_(t)is the length afterexposure for a time, t. Six tresses were tested per hair spraycomposition and the data was statistically analyzed and compared at the95% confidence level. In all the experiments, AMPHOMER was used as theresin in a control hair spray product.

[0127] Hair set retention was measured at 25° C. and a low relativehumidity (i.e., 70% RH). Table 5 summarizes hair set retention tests,and hair crust tests, from hair spray compositions incorporating variouscarboxylated polyurethane resins listed in Table 1. The hair setretention and hair crust test results were compared to the resultsprovided by a control hair spray product containing AMPHOMER. Thecomparative test shows that hair spray compositions containing acarboxylated polyurethane resin having an M_(w) of greater than about30,000 exhibited comparable or better set retention than AMPHOMER. Thehair set retention provided by the carboxylated polyurethane resins,therefore, is considered to be excellent because AMPHOMER is used insuccessful commercial hair spray compositions.

[0128] The ability of the present hair spray composition to hold ahairstyle at high relative humidity (i.e., 85% RH) and 25° C. also weretested by the above-described method. The results are summarized inTable 6. TABLE 6 Example Polyurethane Resin Stiffness and Crust¹⁹ Feel²⁰Flaking²¹ 1 hr. % Set Retention 1 hr. @ 85% RH¹⁷ 11 19 4.77(≠) 5.02(≠)2.92(≠) 65.43 12  20⁵ 4.28(≠) 4.80(≠) 3.75(≠) 55.97 13 21 3.03(≠)2.68(≠) 1.65(≠) 46.07(≠) 14  22⁶ 6.29 8.14 8.34 68.52 15  23⁷ 6.92 8.357.05 89.80(≠) 16  24⁸ 8.29(≠) 9.56(≠) 8.43 91.40(≠) 17 25 6.51 7.23 5.7170.42(≠) 18  26⁹ 4.50(≠) 4.54(≠) 1.82(≠) 63.24 19 27 6.39 8.20 7.1880.00(≠) 20 28 5.53 6.51(≠) 6.69 75.37(≠) 21  29¹⁰ 4.21(≠) 4.48(≠)4.22(≠) 72.98(≠) 22  30¹¹ 4.88(≠) 6.72 7.03 95.13(≠) Control¹⁶ 7.00 7.006.00 62.50

[0129] The results summarized in Table 6 show that, except for Example13, each of the hair spray compositions containing a carboxylatedpolyurethane resin having an M_(w) at least 20,000, e.g., about 20,000to about 70,000, performed as well as or better than the control hairspray product containing AMPHOMER. However, the composition of Example13 imparted the desired properties of low stiffness, crust, and flaking,and a natural feel to treated hair tresses. The hair set retentionprovided by the carboxylated polyurethane resins, therefore, isconsidered to be superior because AMPHOMER is the resin used insuccessful commercial hair spray compositions.

[0130] Sprayed hair also was tested for hair crust, feel, and flaking.The hair crust test measures the hardness and/or stiffness of hairsprayed with a hair spray composition. Hair spray compositions thatprovide natural, or reduced, crusts are desired.

[0131] Hair crust can be tested by compression. In this test, two gramhair tresses were sprayed with one cubic centimeter of a hair spraycomposition. The sprayed tress then was rolled and set on a 2.4centimeter (cm) diameter roller. Six tresses were tested for each hairspray composition. The rolled tresses were equilibrated overnight at 70%RH and 25° C. The tresses then were removed from the rollers andcompressed to 25% strain using a Dia-Stron mini-tensile stress tester.The compression force was measured as gram force. The data wasstatistically analyzed and compared at the 95% confidence level. Theresults are summarized in Table 5.

[0132] The results in Table 5 show that a hair spray compositioncontaining a carboxylated polyurethane resin exhibited lower compressionforces than the control composition containing AMPHOMER. Hair sprayedwith the compositions of Examples 1-10, therefore, had lower crust andbetter feel than hair sprayed with the control composition. Accordingly,the present hair spray compositions outperformed the control compositionin the hair crust test.

[0133] Hair crust also can be tested subjectively. In this test, a groupof trained judges evaluated hair tresses sprayed with a hair spraycomposition containing a polyurethane resin or with the controlcomposition. The data and test procedure are summarized in Table 6.Table 6 shows that overall the present hair spray compositions displayedcomparable or lower crust within experimental error than he standardcontrol composition.

[0134] Table 6 also summarizes data and the test procedure for hairfeel. The data in Table 6 shows that a hair spray composition containinga carboxylated polyurethane resin having an M_(w) of below 65,000, e.g.,about 20,000 to about 65,000, imparted better hand feel properties tosprayed hair than the control composition. It also was found that handfeel properties of sprayed hair was maximized for hair spraycompositions containing a carboxylated polyurethane resin having anM_(w) of less than about 40,000, e.g., about 20,000 to about 40,000, andan R-value below about 0.75, i.e., about 0.40 to about 0.75.

[0135] Hair sprayed with the hair spray compositions also were testedfor the amount of flakes or dust that form on the hair after combinghair that has been sprayed with the composition and dried. Table 6 showsthat, in general, hair spray compositions containing a carboxylatedpolyurethane resin performed equally to the control composition. Inparticular, hair spray compositions containing a carboxylatedpolyurethane resin having an M_(w) of less than about 40,000 and anR-value of less than 0.75 outperformed the control composition.

[0136] Many modifications and variations of the invention ashereinbefore set forth can be made without departing from the spirit andscope thereof, and, therefore, only such limitations should be imposedas are indicated by the appended claims.

What is claimed is:
 1. A hair spray composition comprising: (a) about0.25% to about 6% by weight of a carboxylated polyurethane resin; (b) 0%to about 80% by weight of an alcohol; and (c) about 15% to about 95% byweight water, wherein the carboxylated polyurethane resin has a weightaverage molecular weight of about 15,000 to about 150,000, and is areaction product of a mixture comprising: (i) about 10% Lo about 90% byweight of the mixture of a polyoxyalkylene diol having a number averagemolecular weight of about 400 to about 20,000; (ii) about 0.0% to about20% by weight of the mixture of an alkylene glycol; (iii) about 3% toabout 80% by weight of the mixture of an organic diisocyanate; (iv)about 0.1% to about 30% by weight of the mixture of a2,2-di(hydroxymethyl)-alkanoic acid; and (v) about 0.001% to about 0.95%by weight of the mixture of water, wherein a ratio of isocyanate groupsto hydroxyl groups is about 0.4 to about 1.1.
 2. The composition ofclaim 1 further comprising about 5% to about 30% by weight of apropellant.
 3. The composition of claim 1 wherein the composition isfree of a neutralizing agent for the carboxylated polyurethane resin. 4.The composition of claim 1 having a viscosity of about 1 to about 25centipoise.
 5. The composition of claim 1 wherein the carboxylatedpolyurethane resin has a weight average molecular weight of about 15,000to about 100,000.
 6. The composition of claim 1 wherein the carboxylatedpolyurethane resin has a weight average molecular weight of about 20,000to about 70,000.
 7. The composition of claim 1 wherein the carboxylatedpolyurethane resin has a weight average molecular weight of about 30,000to about 65,000.
 8. The composition of claim 1 wherein the carboxylatedpolyurethane resin has an acid value of at least 7 mg KOH/g resin. 9.The composition of claim 1 wherein the carboxylated polyurethane resinhas a melting point of about 40° C. to about 120° C.
 10. The compositionof claim 1 wherein the polyoxyalkylene diol comprises a blend of two ormore polyoxyalkylene diols.
 11. The composition of claim 1 wherein thepolyoxyalkylene diol is selected from the group consisting of apolyoxyethylene diol having a number average molecular weight of about400 to about 20,000, a polyoxypropylene diol having a number averagemolecular weight of about 200 to about 2,500, a block copolymer ofethylene oxide and propylene oxide having a number average molecularweight of about 1,000 to about 9,000, a polyoxytetramethylene diolhaving a number average molecular weight of about 200 to about 4,000,and mixtures thereof.
 12. The composition of claim 1 wherein thepolyoxyalkylene diol comprises a polyoxyethylene diol having a numberaverage molecular weight of about 6000 to about 10,000.
 13. Thecomposition of claim 12 wherein he polyoxyalkylene diol furthercomprises a polypropylene glycol having a number average molecularweight of about 1,000 to about 3,500, a polyoxyethylene glycol having anumber average molecular weight of about 600 to about 2,500 or a mixturethereof.
 14. The composition of claim 1 wherein the water is present inan amount of about 0.01% to about 0.65%.
 15. The composition of claim 1wherein the alkylene glycol is selected from the group consisting ofethylene glycol, propylene glycol, 2-ethyl1,3-hexanediol, tripropyleneglycol, triethylene glycol, 2,4pentanediol, 1,4-butanediol,2-methyl-1,3-propanediol, cyclohexanediol, cyclohexanedimethanol,2-methyl-1,3-pentadediol, dipropylene glycol, diethylene glycol, andmixtures thereof.
 16. The composition of claim 1 wherein the organicdiisocyanate is an aliphatic diisocyanate.
 17. The composition of claim16 wherein the aliphatic diisocyanate is selected from the groupconsisting of methylene bis(cyclohexyl-4-isocyanate),trimethylhexamethylene diisocyanate, isophorone diisocyanate,tetramethylene duisocyanate, hexamethylene diisocyanate, trimethylenediisocyanate, cyclohexyl-1,2-diisocyanate, cyclohexyl-1,4-diisocyanate,and mixtures thereof.
 18. The composition of claim 1 wherein the 2,2-di(hydroxymethyl) alkanoic acid comprises dimethylolpropionic acid. 19.The composition of claim 1 wherein the 2,2-di (hydroxymethyl) alkanoicacid is present in an amount of about 0.5% to about 2.7% by weight. 20.The composition of claim 1 wherein the water is present in an amount ofabout 0.01% to about 0.8% by weight.
 21. The composition of claim 1wherein the water is present in an amount of about 0.04% to about 0.25%.22. The composition of claim 1 wherein the water is present in an amountof about 0.08% to about 0.45%, by weight, and the ratio of isocyanategroups to hydroxyl groups is about 0.55 to about 0.95.
 23. Thecomposition of claim 1 wherein the water is present in an amount ofabout 0.15% to about 0.45% by weight, and the ratio of isocyanate groupsto hydroxyl groups is about 0.6 to about 0.92.
 24. The composition ofclaim 1 wherein the ratio of isocyanate groups to hydroxyl groups isabout 0.45 to about
 1. 25. The composition of claim 1 wherein the ratioof isocyanate groups to hydroxyl groups is about 0.5 to about 0.98. 26.The composition of claim 1 wherein the carboxylated polyurethane resinhas a weight average molecular weight of about 15,000 to about 40,000and the ratio of isocyanate groups to hydroxyl groups is about 0.4 toabout 0.75.
 27. The composition of claim 2 wherein the propellant isselected from the group consisting of trichlorofluoromethane,dichlorodifluoromethane, dichlorotetrafluoroethane,monochlorodifluoromethane, trichlorotrifluoroethane, dimethyl ether,propane, n-butane, isobutane, dimethyl ether, carbon dioxide, nitrogen,helium, a perfluorinated oxetane, a perfluorinate oxepane, and mixturesthereof.
 28. The composition of claim 1 comprising about 1% to about 3%of the carboxylated polyurethane resin, about 50% to about 60% ethanol,and about 40% to about 45% water.
 29. A method of treating hair to fixthe hair in a desired hairstyle comprising: (a) configuring the hair inthe desired hairstyle; and (b) applying a hair spray composition to thehair, said hair spray composition comprising (i) about 0.25% to about 6%by weight of a carboxylated polyurethane resin; (ii) 0% to about 80% byweight of an alcohol; and (iii) about 15% to about 95% by weight water,wherein the carboxylated polyurethane resin has a weight averagemolecular weight of about 15,000 to about 150,000, and is a reactionproduct of a mixture comprising: (A) about 10% to about 90% by weight ofthe mixture of a polyoxyalkylene diol having a number average molecularweight of about 400 to about 20,000; (B) about 0.01% to about 20% byweight of the mixture of an alkylene glycol; (C) about 3% to about 80%by weight of the mixture of an organic diisocyanate; (D) about 0.% toabout 30% by weight of the mixture of a 2,2-di(hydroxymethyl)alkanoicacid; and (E) about 0.001% to about 0.95% by weight of the mixture ofwater, wherein a ratio of isocyanate groups to hydroxyl groups is about0.4 to about 1.1.
 30. The method of claim 29 wherein the hair spraycomposition further comprises about 5% to about 30% by weight of apropellant.
 31. The method of claim 29 wherein the hair is configured inthe desired hairstyle prior to applying the hair spray composition. 32.The method of claim 29 wherein the hair is configured in the desiredhairstyle after applying the hair spray composition.
 33. The method ofclaim 32 wherein the hair is configured using a curling iron or a blowdryer.